EP0132789B1 - A process for reacting an epoxy resin or a thioepoxide with a polyhydric phenol, a polyhydric thiophenol, a carboxylic acid or a carboxylic acid anhydride - Google Patents

A process for reacting an epoxy resin or a thioepoxide with a polyhydric phenol, a polyhydric thiophenol, a carboxylic acid or a carboxylic acid anhydride Download PDF

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Publication number
EP0132789B1
EP0132789B1 EP84108510A EP84108510A EP0132789B1 EP 0132789 B1 EP0132789 B1 EP 0132789B1 EP 84108510 A EP84108510 A EP 84108510A EP 84108510 A EP84108510 A EP 84108510A EP 0132789 B1 EP0132789 B1 EP 0132789B1
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reaction
carboxylic acid
polyhydric
reactants
thioepoxide
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EP84108510A
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German (de)
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French (fr)
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EP0132789A1 (en
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George A. Doorakian
Joseph W. Hanafin
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5456—Arylalkanephosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus

Definitions

  • Epoxy resins have long been produced by the reaction of a vicinal epoxide with a compound bearing phenolic hydroxyls in the presence of a catalyst in a so-called advancement reaction.
  • catalysts include, for example, tertiary amines, quaternary ammonium halides; phosphonium halides, and phosphonium carboxylates.
  • This invention is directed to a process for reacting at an elevated temperature (a) an epoxy resin or thioepoxide bearing an average of more than one vicinal epoxide or thioepoxide group per molecule with (b) a polyhydric phenol, a polyhydric thiophenol, a carboxylic acid or a carboxylic acid anhydride, characterized by conducting the reaction in the presence of at least 0.01 % by weight of the other reactants of (c) a trihydrocarbyl phosphine or quaternary phosphonium cation which bear on the average per molecule more than one moiety corresponding, to the formula where Z is ⁇ O ⁇ or ⁇ S ⁇ , R 3 at each occurrence is independently a moiety essentially inert in this process, e.g.
  • C, to C 4 alkyl or-CI or ⁇ Brand w is an integer from 0 to 4, so as to promote the reaction of (a) with (b) and (C).
  • These phosphorus compounds are not readily extracted from the resulting resins. Preferably, less than 25 weight percent of the phosphorus compounds initially present in the resulting resin are extracted in refluxing methanol in 12 hours.
  • phosphinophenols phosphinothiophenols and quaternized derivatives thereof are incorporated into the resulting resins via reaction with the epoxides.
  • these phosphorous compounds undergo reaction with epoxides in the subject process, they are referred to herein as initiators rather than catalysts.
  • the resins incorporating moieties derived from these phosphorus compounds are also believed novel.
  • Preferred phosphorus-containing initiators correspond to one of the following formulae I, II and III: wherein R and R2 are each independently or monovalent hydrocarbon radicals, X e is a compatible anion, R 1 is a monovalent hydrocarbon radical optionally including chlorine, bromine, phosphine, phosphonium, phenyl and thiophenyl moieties, Z is independently ⁇ O ⁇ or ⁇ S ⁇ at each occurence, and A is a hydrocarbon radical bearing valences on one or more carbon atoms equal in total to (n+1) where n is an integer 1, 2 or 3.
  • salts of formulae II and III can also be zwitterions, i.e. the anion is formed by deprotonation of one of the groups,
  • the initiator corresponds to the formula wherein m is an integer from 1 to 3, preferably 1 to 2.
  • Preferred initiators correspond to formulae I, II or III presented hereinbefore. Particularly preferred are compounds wherein R and R 2 are each independently phenyl, thiophenyl or hydroxyphenyl; R 1 is phenyl or C 1 to C 4 alkyl; A is an (n+1)-valent alkyl radical having 1 to 12 carbon atoms; n is 2; w is 0, and X ⁇ is fluoride, bromide, chloride, iodide, carboxylate (such as acetate), bicarbonate, bisphosphate, phenate or bisphenate anion. Preferably, each initiator bears a total of two hydroxyphenyl or thiophenyl moieties.
  • Initiators bearing only one hydroxyphenyl or thiophenyl group produce resins of low molecular weight, whereas those bearing more than two such groups produce cross-linked resins when employed at high concentrations.
  • Z at each occurrence in formulae I, II and III is -0-.
  • Preferred compounds of Formula III can generally be prepared by the following reaction. wherein q is an integer from 1 to 20 and the catalyst can be BF 3 .
  • the compounds of formula III can also generally be prepared by the following reaction: wherein q is an integer from 1 to 20 and T is CI or Br. Anion exchange is possible to produce salts with other anions.
  • Still other compounds of formula II can typically be prepared by the following reaction. wherein q and T are as described hereinbefore.
  • diluents are aromatic hydrocarbon, e.g., xylene. Temperatures from 25°C to 180°C are in general suitable for the preparation of this subject initiators.
  • the phosphinophenols and their quaternary derivatives are generally white or yellow crystalline solids. These solids are generally soluble or slightly soluble in moderately poor solvents.
  • the subject initiators can be reacted with vicinal epoxide reactants in the same manner as other phenol or thiophenol reactants, except that these initiators do not require a separate catalyst when used at catalytically effective loadings.
  • other polyhydric phenols not containing phosphorus moieties would be reacted with the epoxide present at the same time as the initiators.
  • the most useful epoxides for reaction with the subject initiators are the polyepoxides, particularly epoxy resin. These polyepoxides are reacted with polyhydric phenols (compounds having more than one phenolic hydroxy group) to form a phenolic hydroxy ether in a so-called advancement reaction.
  • the polyepoxide reactants are organic compounds possessing more than one 1,2-epoxide group per molecule. These polyepoxides can be saturated or unsaturated aliphatic or cycloaliphatic, aromatic or heterocyclic in nature. Additionally, the polyepoxides can bear substituents which are inert in the advancement reaction, such as ether or halogen moieties.
  • polyepoxides that may be used in the invention are given in US 2,633,458.
  • the polyepoxides are conveniently described in terms of epoxy equivalent values, as defined in this patent.
  • the polyepoxides used in the subject advancement reaction are those having an epoxy equivalent greater than 1.0.
  • polyepoxides include the glycidyl ethers of novolac resins, i.e., phenol-aldehyde condensates.
  • Preferred resins of this type are those of the formula IV: wherein each R 4 independently is hydrogen or an alkyl radical and j has an average value of from 0.1 to 10, preferably from 1 to 2. Preparation of these polyepoxides is illustrated in US 2,616,099 and 2,658,885.
  • "Y" preferably is an alkylene or alkylidine group having from 1 to 4 carbon atoms. In another preferred embodiment, "Y" is derived from the initiators corresponding to formulae I, II or III.
  • polyepoxides include the epoxidized esters of the polyethylenically unsaturated monocarboxylic acids, such as epoxidized linseed, soybean, perilla, oiticica, tung, walnut and dehydrated castor oil, methyl linoeate, butyl linoeate, ethyl 9,12-octadecanedioate, butyl 9,12,15-octadecanetrioate, butyl olestearate, mono- or diglycerides of tung oil, monoglycerides of soybean oil, sunflower oil, rapeseed oil, hempseed oil, sardine oil, and cottonseed oil.
  • epoxidized esters of the polyethylenically unsaturated monocarboxylic acids such as epoxidized linseed, soybean, perilla, oiticica, tung, walnut and dehydrated castor oil, methyl linoe
  • Sulfur analogs of glycidyl ether groups i.e. compounds bearing are also operable.
  • the phenolic and thiophenolic reactants are organic compounds having one or more hydroxyl or thiol groups attached to an aromatic carbocyclic nucleus.
  • This class of compounds therefore includes thiophenol, phenol, alpha and beta naphthol, o-, m-, or p-chlorophenol, alkylated derivatives of phenol (e.g., o-methyl-, 3,5-dimethyl-, p-t-butyl- and p-nonylphenol) and other monohydric phenols as well as polyhydric phenols; such as resorcinoi, hydroquinone, dithiophenol ; p-p'-dimercaptophenyl ether, p,p'-dimercaptobiphenyl, and p-hydroxythiophenol.
  • phenolic reactants can be employed. However, phenolic reactants are generally preferred.
  • the polyhydric phenols bearing from 2 to 6 hydroxyl groups and having from 6 to 30 carbon atoms are particularly useful as reactants in the reaction with epoxy resins to form high molecular weight resins.
  • Representative of these preferred phenols are 2,4', 4"-tri(hydroxyphenyl)methane and phenolphthalein.
  • Particularly preferred as phenol reactants are those compounds corresponding to formula V.
  • the most preferred phenols are bisphenol A(4-4'-isopropylidenediphenol), bisphenol F (4,4'-methylenediphenol), 2,2', 6,6'-tetrachlorobisphenol A, 2,2',6,6'-tetrabromobisphenol A, bisphenol S (4,4'-sulfonyldiphenol). 4,4'-dihydroxybiphenyland 2,2'-diallyl bisphenol A.
  • Bisphenol A is the polyhydric phenol of choice.
  • the subject phosphorus-containing initiators are themselves phenolic or thiphenolic reactants. These initiators comprise up to 100 mole percent of the total phenolic and thiophenolic reactants present, preferably comprise no more than 10 mole percent of these reactants.
  • the organic carboxylic acids and anhydrides are likewise well known.
  • the acids bear one or more carboxyl groups on the organic nucleus.
  • the anhydrides are prepared from such carboxylic acids by the removal of water therefrom in an intra-or intermolecular condensation.
  • This class of compounds therefore includes acetic, propionic, octanoic, stearic, acrylic, methacrylic, oleic, benzoic, phthalic, isophthalic, maleic, succinic, adipic, itaconic, polyacrylic and polymethacrylic acids, and anhydrides thereof, such as acetic anhydride, phthalic anhydride, and hexahydrophthalic anhydride.
  • a preferred subclass of acids is comprised of members which are useful in cross-linking epoxy resins.
  • the members of this subclass are normally di- or tribasic acids, or anhydrides thereof, and are preferably liquid or low melting solids such as succinic, maleic, or hexahydrophthalic acids or anhydrides.
  • Other such acids and anhydrides are shown, for example, in US 2,970,983 and 3,547,885.
  • resins prepared from the reaction of epoxides with phenols or thiophenols have more diverse utilities than those prepared from carboxylic acids or anhydrides.
  • reaction conditions employed in the process may be varied. Generally, however, convenient rates of reaction are obtained at reation temperatures in the range.of from 50°C to 300°C and reaction pressures ranging from about subatmospheric (0.1 millimeter Hg or 13 Pa) to about 150 psig (1034 kPa).
  • the ratio of the epoxide to the phenol, thiophenol or carboxylic acid or anhydride reactants to be employed in the process may vary over a wide range depending upon the type of reactants and the type of product desired. For example, if a product terminated with a phenolic hydroxyl group is desired, one would employ an excess of the polyhydric phenol in the process.
  • the amount of the phosphorus-containing initiator employed in the process of this invention can likewise vary over a wide range, so long as an effective amount is present.
  • the initiator is added in amounts of at least 0.01 percent, preferably from 0.1 percent to 10 percent, by weight of the other reactants.
  • the reaction may be conducted in the presence or absence of solvents or diluents, but is conveniently conducted in a liquid phase.
  • the reactants will be liquid or low melting solids and the reaction may be at least initially easily effected without the addition of solvents or diluents.
  • the reaction mixture becomes progressively more viscous and may solidify.
  • it may be necessary to add diluents, increase the temperature of the reaction mixture to the fusion point of the reactants or to utilize very efficient blending means.
  • Suitable diluents are those organic compounds which are inert to the reactants and in the liquid phase at the reaction temperature, for example, ethylene glycol ethyl ether, xylene, toluene, and cyclohexane.
  • the diluent is desirably substantially free of impurities which will decrease the activity of the catalyst, such as hydrogen peroxide or uncomplexed transition metal ions and moieties which react with phosphonium ylids, e.g., water, aldehydes and ketones.
  • the solvent may be retained in the reaction mixture. Otherwise, the solvent can be removed by any suitable method such as distillation.
  • substantially equivalent quantities of polyhydric phenol (or thiophenol) and polyepoxide reactants should be employed in the overall reaction (i.e., no more than about 2 percent excess of either reactant).
  • polyepoxide and the polyhydric phenol approaches completion, it is desirable, but not essential, to introduce sufficient tetrabromobisphenol A to react the vicinal epoxy groups completely and to increase molecular weight of the product in the manner taught in US 4,104,257.
  • the products obtained by reacting a polyepoxide with a phenol in the presence of the described initiators are phenolic hydroxy ether compounds. Their physical characteristics will depend upon the reactants and proportions employed. In general, the products will vary from liquids to solids, and in the case of the high molecular weight resins will vary from viscous liquids to hard solids.
  • the products will possess an aliphatic OH group formed by each reaction of an epoxide and a phenolic OH group, and can be further reacted through this group if desired.
  • the polyfunctional reactants will also give products terminated in phenolic OH groups and/or epoxy groups, and these will be available for further reaction. For example, if the initiator bears more than two aromatic hydroxy groups, the product will have branched or cross-linked structure.
  • the control of the equivalent ratio of the polyepoxides and polyhydric phenols during the advancement reaction permits the preparation of a variety of products. Those products which use an excess of the polyepoxide in their preparation will be terminated in epoxy groups and can be used as polyepoxides in known reactions of polyepoxides with curing agents.
  • the high molecular weight polyepoxides are particularly useful in preparing surface coatings, adhesives, laminates, filament windings, coatings for highways and airfields, structural applications, and formations of foams. Those prepared from the halogenated polyhydric phenols or containing a large weight percentage of phosphorus moieties are particularly useful as flame-proofing resins for forming laminates coatings.
  • the advanced resins are prepared under essentially anhydrous conditions (eliminating essentially all water from the reactants) and at temperatures less than 170°C, the phosphorus moieties though polymer-bound retain catalytic activity.
  • the reaction conditions are further described in US 4,438,254. These resins exhibit accelerated curing with amines and anhydrides.
  • Resins prepared at higher temperatures or in the presence of water will generally contain phosphorus moieties present as polymer-bound tertiary phosphine oxides or phosphonium cations. These moieties exhibit little catalytic activity but improve ignition retardance of the resin.
  • the reaction products terminated in epoxy groups can also be used to prepare vinyl ester resins.
  • Vinyl ester resins are described in U.S. 3,367,992 wherein dicarboxylic acid half esters of hydroxyalkyl acrylates or methacrylates are reacted with polyepoxide resins.
  • US 3,066,112 and 3,179,623 describes the preparation of vinyl ester resins from unsaturated monocarboxylic acids such as acrylic and methacrylic acid.
  • Vinyl ester resins based on epoxy novolac resins are described in US 3,301,743.
  • the unsaturated monocarboxylic acids which can be reacted with a polyepoxide in the presence of the described catalysts to prepare a vinyl ester resin include, for example, acrylic acid, methacrylic acid, halogenated acrylic acid or methacrylic acid, cinnamic acid and mixtures thereof, and hydroxyalkyl acrylate or methacrylate half esters of dicarboxy acids as described in US 3,367,992, wherein the hydroxyalkyl group preferably has from 2 to 6 carbon atomes.
  • the products prepared by the reaction of epoxides with thiophenols are generally similar in properties and utilities to those prepared from phenols.
  • the thiophenol-derived resins exhibit higher molecular weights than their phenolic counterparts.
  • Tri(p-hydroxyphenyl)phosphine (4 g, 1.29 millimole (mmole)) was stirred in 150 ml absolute ether at room temperature in a250 ml round-bottom flask. Methyl iodide (2.75 g, 19.4 mmol, 1.21 ml) was added, and the solution stirred overnight. A test for unreacted phosphine in the ether solution (maleic anhydride in acetone) was negative, and the product was filtered off as a white precipitate and vacuum dried at room temperature overnight giving 5.76 g of tru(p-hydroxyphenyl)methylphosphonium iodide (98.8% yield). NMR (CD 3 0D); ⁇ (ppm, TMS) 2.80 (d, 3H, CH 3 ), 6.82-7.52 (m, 12H, arom.).
  • methyl di(p-hydroxypnenyl)phenyl phosponhonium iodide was prepared using phenyldichlorophosphine in place of phosphorus trichloride.
  • methyl(p-hydroxyphenyl)diphenyl phosphonium iodide was prepared using diphenylchlorophosphine in place of phosphorus trichloride.
  • Tri(p-hydroxyphenyl)phosphine hydrobromide, methyl di(p-hydroxyphenyl)phenyl phosphonium iodide and methyl(p-hydroxyphenyl)diphenyl phosphium iodide were used to promote the reaction of bisphenol - A and a commercial epoxy resin prepared from bisphenol A and epichlorohydrin and having an epoxy equivalent weight between 177 and 188.
  • This epoxy resin is sold by the Dow Chemical Company under the trademark of D.E.R. 330®.
  • To a flask equipped with a stirrer, thermometer, heating mantle and nitrogen purge line was charged 224.2 grams of D.E.R 330 ® epoxy resin and 75.8 grams of bisphenol A. The mixture was heated with stirring to 50°C and then 0.3 or 3.0 grams of each initiator in 20 milliliters (ml) of methanol were added in separate runs.
  • the resulting resin was determined to contain 2.90 percent epoxide. No phosphorus compounds were extracted from the resin in refluxing methanol.
  • the resulting resin was determined to contain 7.88 percent epoxide. No phoshorus compounds were extracted from the resin in refluxing methanol.
  • Example 9 To a reaction vessel were charged the same epoxy resin and dihydric phenol as in Example 9 in a ratio which in theory should produce an advanced resin containing 1.0 percent epoxide. To this mixture was added methyl di(p-hydroxyphenyl)phenyl phosphonium acetate in a ratio of 0.4 part phr. The advancement reaction was conducted in the general manner of Example 4.
  • the resulting resin was determined to contain 1.22 percent epoxide. No phosphorus compounds were extracted from the resin in refluxing methanol.

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EP84108510A 1983-07-21 1984-07-19 A process for reacting an epoxy resin or a thioepoxide with a polyhydric phenol, a polyhydric thiophenol, a carboxylic acid or a carboxylic acid anhydride Expired EP0132789B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/515,824 US4477645A (en) 1983-07-21 1983-07-21 Immobilized epoxy advancement initiators
US515824 1983-07-21

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EP0132789A1 EP0132789A1 (en) 1985-02-13
EP0132789B1 true EP0132789B1 (en) 1987-12-09

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US (1) US4477645A (enExample)
EP (1) EP0132789B1 (enExample)
JP (1) JPS60500962A (enExample)
KR (1) KR910006813B1 (enExample)
AU (1) AU554910B2 (enExample)
CA (1) CA1230194A (enExample)
DE (1) DE3468034D1 (enExample)
ES (1) ES8605003A1 (enExample)
SG (1) SG75989G (enExample)
WO (1) WO1985000612A1 (enExample)

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ES534498A0 (es) 1985-10-01
JPS632972B2 (enExample) 1988-01-21
US4477645A (en) 1984-10-16
ES8605003A1 (es) 1985-10-01
KR850001249A (ko) 1985-03-16
KR910006813B1 (ko) 1991-09-02
DE3468034D1 (en) 1988-01-21
JPS60500962A (ja) 1985-06-27
EP0132789A1 (en) 1985-02-13
WO1985000612A1 (en) 1985-02-14
CA1230194A (en) 1987-12-08
SG75989G (en) 1990-04-20
AU3214984A (en) 1985-03-04
AU554910B2 (en) 1986-09-04

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